High-temperature spectra of the PNO molecule based on robust first-principles methods

Abstract

The PNO molecule is an important species found in the interstellar medium, and its spectroscopic information is helpful for its detection. We present the first line list of PNO (X¹Σ⁺) using robust first-principles methods. The analytical potential energy surface and the dipole moment surface were constructed based on 11 942 ab initio points. The variational nuclear motion calculation was implemented in TROVE to obtain the rovibrational energy levels, Einstein A coefficients and other parameters. The J-dependent Coriolis-decoupled Hamiltonian was adopted with k ≤ 15, and the l-type doubling was considered for the bending vibration of the linear molecule. The line list contained almost 5.87 billion transitions between 3.61 million levels with rotational excitation up to J = 200 and was used to generate the PNO spectrum below 3000 K in the wavenumber range from 0 to 6000 cm⁻¹. The millimetre wave spectrum agrees well with available experimental benchmarks. The Fermi resonance effects in the PNO spectrum are universal and complex, resulting in significant intensity increment of the related weak transition. This line list may be helpful for the spectroscopic characterization and possible astronomical detection of PNO, especially in high-temperature environments.